WO2012120897A1 - Film de retard, plaque polarisante, dispositif d'affichage à cristaux liquides et composé - Google Patents

Film de retard, plaque polarisante, dispositif d'affichage à cristaux liquides et composé Download PDF

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Publication number
WO2012120897A1
WO2012120897A1 PCT/JP2012/001641 JP2012001641W WO2012120897A1 WO 2012120897 A1 WO2012120897 A1 WO 2012120897A1 JP 2012001641 W JP2012001641 W JP 2012001641W WO 2012120897 A1 WO2012120897 A1 WO 2012120897A1
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group
acid
general formula
retardation film
alkyl group
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PCT/JP2012/001641
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English (en)
Japanese (ja)
Inventor
鈴木　隆嗣
一成 中原
宏佳 木内
福坂　潔
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コニカミノルタアドバンストレイヤー株式会社
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Priority to CN201280022415.8A priority Critical patent/CN103518151B/zh
Priority to KR1020137023539A priority patent/KR101558722B1/ko
Priority to US14/003,565 priority patent/US8936840B2/en
Priority to JP2013503402A priority patent/JP5920336B2/ja
Publication of WO2012120897A1 publication Critical patent/WO2012120897A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/06—Cellulose acetate, e.g. mono-acetate, di-acetate or tri-acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/16—Preparation of mixed organic cellulose esters, e.g. cellulose aceto-formate or cellulose aceto-propionate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3462—Six-membered rings
    • C08K5/3465—Six-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/12—Cellulose acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/14—Mixed esters, e.g. cellulose acetate-butyrate
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/08—Cellulose derivatives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
    • C09K2323/03—Viewing layer characterised by chemical composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
    • C09K2323/03—Viewing layer characterised by chemical composition
    • C09K2323/031—Polarizer or dye
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
    • C09K2323/03—Viewing layer characterised by chemical composition
    • C09K2323/035—Ester polymer, e.g. polycarbonate, polyacrylate or polyester

Definitions

  • the present invention relates to a retardation film, a polarizing plate, a liquid crystal display device and a compound.
  • the retardation film is used for expanding the viewing angle and improving the contrast in the liquid crystal display device.
  • liquid crystal panels have been made thinner and liquid crystals in liquid crystal cells have been improved to improve the response speed of liquid crystal display devices, reduce weight, and reduce manufacturing costs. Is required.
  • a thin film as a means for achieving cost reduction by high-speed production and lengthening of a retardation film.
  • even higher performance is required for retardation films.
  • the thickness of the film is extremely thin, it has, for example, a large retardation performance and mechanical strength that does not cause any problems in handling. It is required to have.
  • the liquid crystal panel becomes thinner, the distance between the backlight and the polarizing plate is shortened and the influence of heat generated from the backlight unit is increased, so even a thin film must have better durability than before. It is done.
  • a film containing a cellulose derivative is widely used as a retardation film because it is excellent in moisture permeability required for producing a polarizing plate.
  • a cellulose ester having a low total substitution degree of acyl groups is used, a compound having a retardation expression effect is added to the film, A technique for stretching the film has been proposed (see, for example, Patent Documents 1 to 3).
  • Patent Documents 1 to 3 the present inventors have found that these methods have insufficient retardation and have problems in mechanical strength in a thin retardation film. It was found that there was a problem with durability.
  • an object of the present invention is to provide a compound that exhibits high retardation.
  • Another object of the present invention is to provide a retardation film having high retardation expression and good mechanical strength and durability.
  • another object of the present invention is to provide a polarizing plate including the retardation film and a liquid crystal display device including the retardation film, having a wide viewing angle and excellent durability.
  • a retardation film containing a cellulose derivative and at least one compound represented by the following general formula (1) is achieved by the following configurations.
  • R 1 and R 2 each independently represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group;
  • X 1 represents a single bond, —NR 4 —, —O— or —S—;
  • X 2 represents a single bond, —NR 5 —, —NR 5 — (C ⁇ O) —, —O— or —S—;
  • R 4 and R 5 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group;
  • R 3 represents a substituent;
  • n represents an integer of 0 to 4; when n is 2 or more, a plurality of R 3 may be the same or different, and adjacent R 3 may be bonded to each other to form a ring.
  • R 9 is selected from the group consisting of a q-valent alkyl group, a q-valent cycloalkyl group, a q-valent aryl group or a q-valent heterocyclic group, or an alkyl group, a cycloalkyl group, an aryl group and a heterocyclic group.
  • R 10 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group;
  • q represents 2 or 3)
  • R 1 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group;
  • X 1 represents a single bond, —NR 4 —, —O— or —S—;
  • X 2 represents a single bond, —NR 5 —, —NR 5 — (C ⁇
  • R 6 is selected from the group consisting of a p-valent alkyl group, a p-valent cycloalkyl group, a p-valent aryl group or a p-valent heterocyclic group, or an alkyl group, a cycloalkyl group, an aryl group and a heterocyclic group.
  • R 7 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group;
  • p represents 2 or 3)
  • the retardation film according to [2], wherein the compound represented by the general formula (3) is a compound represented by the following general formula (4).
  • R 1 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group
  • X 1 represents a single bond, —NR 4 —, —O— or —S—
  • R 4 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group
  • R 3 represents a substituent
  • n represents an integer of 0 to 4; when n is 2 or more, a plurality of R 3 may be the same or different, and adjacent R 3 may be bonded to each other to form a ring.
  • J is selected from the group consisting of a divalent alkyl group, a divalent cycloalkyl group, a divalent aryl group or a divalent heterocyclic group, or an alkyl group, a cycloalkyl group, an aryl group and a heterocyclic group.
  • the in-plane retardation Ro represented by the following formula is 40 to 100 nm and the thickness direction retardation Rth is 100 to The retardation film according to any one of [1] to [4], which is 300 nm.
  • a polarizing plate comprising a polarizer and the retardation film according to any one of [1] to [7] disposed on at least one surface of the polarizer.
  • a liquid crystal display device comprising the retardation film according to any one of [1] to [7].
  • a liquid crystal display device having a liquid crystal cell and the polarizing plate according to [8] disposed on at least one surface of the liquid crystal cell.
  • a retardation film comprising a compound represented by the following general formula (1).
  • R 1 and R 2 each independently represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group;
  • X 1 represents a single bond, —NR 4 —, —O— or —S—;
  • X 2 represents a single bond, —NR 5 —, —NR 5 — (C ⁇ O) —, —O— or —S—;
  • R 4 and R 5 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group;
  • R 3 represents a substituent;
  • n represents an integer of 0 to 4; when n is 2 or more, a plurality of R 3 may be the same or different, and adjacent R 3 may be bonded to each other to form a ring.
  • R 1 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group
  • X 1 represents a single bond, —NR 4 —, —O— or —S—
  • R 4 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group
  • R 3 represents a substituent
  • n represents an integer of 0 to 4; when n is 2 or more, a plurality of R 3 may be the same or different, and adjacent R 3 may be bonded to each other to form a ring.
  • J is selected from the group consisting of a divalent alkyl group, a divalent cycloalkyl group, a divalent aryl group or a divalent heterocyclic group, or an alkyl group, a cycloalkyl group, an aryl group and a heterocyclic group.
  • a compound that expresses high retardation can be provided.
  • a retardation film having high retardation development property and good mechanical strength and durability can be provided.
  • a polarizing plate including the retardation film and a liquid crystal display device including the retardation film, having a wide viewing angle, and excellent durability can be provided.
  • the present inventors diligently studied a retardation film containing various low molecular compounds and a cellulose derivative. As a result, although the detailed reason has not been elucidated, it has been found that a specific quinazoline compound has extremely high retardation expression. Furthermore, it has been found that by using this quinazoline compound, a retardation film having high retardation expression and good mechanical strength and durability can be obtained. Further, it has been found that when the retardation film is used, a liquid crystal display device having a wide viewing angle and excellent durability can be obtained.
  • the quinazoline compound is an aromatic compound having a structure in which two 6-membered rings, a benzene ring and a pyrimidine ring, are condensed.
  • bonded with 2nd-position and 4th-position was used, it discovered that the said subject could be solved and it came to this invention.
  • R 1 and R 2 each represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group.
  • the number of carbon atoms of the alkyl group represented by R 1 and R 2 is preferably 1-18, and more preferably 1-8.
  • the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, a pentyl group, a hexyl group, an octyl group, a dodecyl group, and a trifluoromethyl group.
  • the cycloalkyl group represented by R 1 and R 2 preferably has 3 to 10 carbon atoms.
  • Examples of the cycloalkyl group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl, an adamantyl group, and the like.
  • the aryl group represented by R 1 and R 2 preferably has 6 to 10 carbon atoms.
  • Examples of the aryl group include a phenyl group and a naphthyl group.
  • Examples of the heterocyclic group represented by R 1 and R 2 include a pyridyl group, a thiazolyl group, an oxazolyl group, a pyrazolyl group, and an imidazolyl group.
  • the alkyl group, cycloalkyl group, aryl group or heterocyclic group represented by R 1 and R 2 may have a substituent.
  • the substituent is not particularly limited, and examples thereof include alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, trifluoromethyl group).
  • cycloalkyl group eg, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, etc.
  • aryl group eg, phenyl group, naphthyl group, etc.
  • acylamino group eg, acetylamino group, benzoylamino group
  • alkylthio groups eg methylthio group, ethylthio group etc.
  • arylthio groups eg phenylthio group, naphthylthio group etc.
  • alkenyl groups eg vinyl group, 2-propenyl group, 3-butenyl group, 1-methyl group) -3-propenyl group, 3-pentenyl group, 1-methyl-3-butenyl , 4-hexenyl group, cyclohexenyl group, etc.
  • halogen atom eg, fluorine atom, chlorine atom, bro
  • R 1 and R 2 are preferably a cycloalkyl group, an aryl group or a heterocyclic group, and more preferably an aryl group.
  • X 1 represents a single bond, —NR 4 —, —O— or —S—.
  • X 2 represents a single bond, —NR 5 —, —NR 5 — (C ⁇ O) —, —O— or —S—.
  • R 4 and R 5 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group.
  • the alkyl group, cycloalkyl group, aryl group or heterocyclic group represented by R 4 and R 5 is an example of the alkyl group, cycloalkyl group, aryl group or heterocyclic group represented by R 1 and R 2 in the general formula (1).
  • These groups may further have a substituent.
  • substituents include an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group represented by R 1 and R 2 in the general formula (1).
  • the group similar to the substituent which you may have can be mentioned.
  • X 1 is -NR 4 - is preferably, -NR 4 - R 4 in is more preferably a hydrogen atom.
  • X 2 is preferably a single bond or —NR 5 —, and more preferably a single bond.
  • R 5 in —NR 5 — is preferably a hydrogen atom.
  • R 3 represents a substituent.
  • substituents represented by R 3 for example, an alkyl group represented by R 1 and R 2 in the general formula (1), a cycloalkyl group, which may have an aryl group or a heterocyclic group
  • R 3 represents a substituent.
  • n represents an integer of 0 to 4.
  • the plurality of R 3 may be the same or different, and adjacent R 3 may be bonded to each other to form a ring.
  • the compound represented by the general formula (1) according to the present invention is preferably a compound represented by the general formula (2) or (3).
  • R 2, R 3, n, X 1, X 2 is the general formula of (1) R 2, R 3 , n, X 1, X 2 and respectively the same.
  • X 1 is preferably —NR 4 —, and R 4 is preferably a hydrogen atom.
  • R 9 represents a q-valent alkyl group, a q-valent cycloalkyl group, a q-valent aryl group or a q-valent heterocyclic group; an alkyl group, a cycloalkyl group, an aryl group and a heterocyclic group.
  • R 10 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group.
  • the q-valent alkyl group represented by R 9 preferably has 1 to 18 carbon atoms, and more preferably 1 to 8 carbon atoms.
  • Examples of the divalent alkyl group represented by R 9 include a methylene group, 1,2-ethylene group, 1,2-propylene group, 1,3-propylene group, 1,4-butylene group and the like.
  • Examples of the trivalent alkyl group include a propane-1,2,3-triyl group and a hexane-1,5,6-triyl group.
  • the q-valent cycloalkyl group represented by R 9 preferably has 3 to 10 carbon atoms.
  • Examples of the divalent cycloalkyl group represented by R 9 include 1,2-cyclohexylene group and 1,4-cyclohexylene group.
  • Examples of the trivalent cycloalkyl group include, for example, Examples thereof include a cyclohexane-1,3,5-triyl group and an adamantane-1,3,5-triyl group.
  • the q-valent aryl group represented by R 9 preferably has 6 to 14 carbon atoms.
  • Examples of the divalent aryl group represented by R 9 include 1,4-phenylene group, 1,3-phenylene group, 1,4-naphthylene group, 2,6-naphthylene group, 9,10-anthracenylene, and the like.
  • Examples of the trivalent aryl group include a benzene-1,3,5-triyl group.
  • Examples of the divalent heterocyclic group represented by R 9 include 2,5-pyridylene group, 1,3-imidazolene group, 3,5-thienylene group, 2,5-thienylene, 2,5-furylene and the like.
  • Examples of the trivalent heterocyclic group include a pyridine-2,4,6-triyl group.
  • the q-valent alkyl group, q-valent cycloalkyl group, q-valent aryl group or q-valent heterocyclic group represented by R 9 may have a substituent.
  • the substituent is not particularly limited, for example, in the general formula (1) alkyl group represented by R 1 and R 2, a cycloalkyl group, an aryl group or a heterocyclic group similar to the substituent which may have The group can be mentioned.
  • Examples of the alkyl group, cycloalkyl group, aryl group or heterocyclic group represented by R 10 include, for example, the alkyl group, cycloalkyl group, aryl group or heterocyclic group represented by R 1 and R 2 in the general formula (1).
  • These groups may further have a substituent.
  • substituents include an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group represented by R 1 and R 2 in the general formula (1).
  • R 1 and R 2 in the general formula (1).
  • the group similar to the substituent which you may have can be mentioned.
  • R 9 is preferably a divalent alkyl group, a divalent cycloalkyl group, a divalent aryl group, or a divalent heterocyclic group.
  • q represents an integer of 2 to 3. q is preferably 2.
  • R 1, R 3, n, X 1, X 2 is R 1 in the general formula (1), R 3, n , and X 1, X 2 respectively the same.
  • X 1 is preferably —NR 4 —, and R 4 is preferably a hydrogen atom.
  • R 6 represents a p-valent alkyl group, a p-valent cycloalkyl group, a p-valent aryl group or a p-valent heterocyclic group; an alkyl group, a cycloalkyl group, an aryl group and a heterocyclic group.
  • R 7 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group.
  • the p-valent alkyl group represented by R 6 preferably has 1 to 18 carbon atoms, and more preferably 1 to 8 carbon atoms.
  • Examples of the divalent alkyl group represented by R 6 include a methylene group, 1,2-ethylene group, 1,2-propylene group, 1,3-propylene group, 1,4-butylene group, and the like.
  • Examples of the trivalent alkyl group include a propane-1,2,3-triyl group and a hexane-1,5,6-triyl group.
  • the p-valent cycloalkyl group preferably has 3 to 10 carbon atoms.
  • Examples of the divalent cycloalkyl group represented by R 6 include a 1,2-cyclohexylene group and a 1,4-cyclohexylene group.
  • Examples of the trivalent cycloalkyl group include, for example, Examples thereof include a cyclohexane-1,3,5-triyl group and an adamantane-1,3,5-triyl group.
  • the p-valent aryl group preferably has 6 to 14 carbon atoms.
  • Examples of the divalent aryl group represented by R 6 include 1,4-phenylene group, 1,3-phenylene group, 1,4-naphthylene group, 2,6-naphthylene group, 9,10-anthracenylene, and the like.
  • Examples of the trivalent aryl group include a benzene-1,3,5-triyl group.
  • Examples of the divalent heterocyclic group represented by R 6 include 2,5-pyridylene group, 1,3-imidazolene group, 3,5-thienylene group, 2,5-thienylene, 2,5-furylene and the like.
  • Examples of the trivalent heterocyclic group include a pyridine-2,4,6-triyl group.
  • the p-valent alkyl group, p-valent cycloalkyl group, p-valent aryl group or p-valent heterocyclic group represented by R 6 may further have a substituent.
  • the substituent is not particularly limited, for example, in the general formula (1) alkyl group represented by R 1 and R 2, a cycloalkyl group, an aryl group or a heterocyclic group similar to the substituent which may have The group can be mentioned.
  • Examples of the alkyl group, cycloalkyl group, aryl group or heterocyclic group represented by R 7 include, for example, the alkyl group, cycloalkyl group, aryl group or heterocyclic group represented by R 1 and R 2 in the general formula (1).
  • These groups may further have a substituent.
  • substituents include an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group represented by R 1 and R 2 in the general formula (1).
  • R 1 and R 2 in the general formula (1).
  • the group similar to the substituent which you may have can be mentioned.
  • R 6 is preferably a p-valent cycloalkyl group, a p-valent aryl group or a p-valent heterocyclic group, a divalent cycloalkyl group, a divalent aryl group or 2
  • a valent heterocyclic group is more preferable, and a divalent aryl group is particularly preferable.
  • p represents 2 or 3. p is preferably 2.
  • the compound represented by the general formula (3) is particularly preferably a compound represented by the general formula (4).
  • R 1, R 3, n, X 1 is the same meaning R 1, R 3, n, X 1 and in the general formula (3).
  • X 1 is preferably —NR 4 —, and R 4 is preferably a hydrogen atom.
  • J represents a divalent alkyl group, a divalent cycloalkyl group, a divalent aryl group or a divalent heterocyclic group; or an alkyl group, a cycloalkyl group, an aryl group and a heterocyclic group.
  • Examples of the divalent alkyl group, divalent cycloalkyl group, divalent aryl group and divalent heterocyclic group represented by J include a divalent alkyl group represented by R 6 in the general formula (3), 2 Examples thereof include the same groups as those exemplified as the examples of the valent cycloalkyl group, the divalent aryl group, and the divalent heterocyclic group. These groups may further have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group represented by R 1 and R 2 in the general formula (1). The group similar to the substituent which you may have can be mentioned.
  • J represents a divalent linking group formed by combining two or more selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group and a heterocyclic group, an alkyl group, a cycloalkyl group, an aryl group or
  • the heterocyclic group is a group consisting of —NR 12 —, —O—, —S—, —C ( ⁇ O) —, —S ( ⁇ O) 2 —, —CH ⁇ CH— and —C ⁇ C—, respectively.
  • At least one divalent linking group selected from the above may be combined inside.
  • R 12 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group.
  • alkyl group, cycloalkyl group, aryl group or heterocyclic group represented by R 12 include, for example, the alkyl group, cycloalkyl group, aryl group or heterocyclic group represented by R 1 and R 2 in the general formula (1).
  • the group similar to the group demonstrated can be mentioned.
  • These groups may further have a substituent.
  • the substituent include an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group represented by R 1 and R 2 in the general formula (1).
  • the group similar to the substituent which you may have can be mentioned.
  • J is preferably a divalent linking group selected from a divalent cycloalkyl group, a divalent aryl group, a divalent heterocyclic group, or a combination of these groups, A divalent aryl group or a combination of these groups is more preferred.
  • the compounds represented by the general formulas (1) to (4) according to the present invention can be produced with reference to known methods. For example, it can be synthesized with reference to the methods described in Synthesis 1981 (1), 35-36, Journal of the American Chemical Society, 1931, 53 (10), 3867-3875, and the like.
  • the compound represented by the general formula (1) of the present invention can be preferably used as a retardation increasing agent.
  • the retardation increasing agent is a film having a retardation of 1 to 15% by mass, preferably 2 to 10% by mass, based on the cellulose derivative, compared with the retardation when no retardation increasing agent is added.
  • the retardation film of this invention contains the compound represented by the above-mentioned general formula (1).
  • the retardation film of the present invention preferably contains a resin and a compound represented by the general formula (1).
  • the compound represented by the general formula (1) may be a compound represented by any one of the general formulas (2) to (4). Further, the compound represented by the general formula (1) may be one kind or a mixture of two or more kinds.
  • the resin that is the main component of the retardation film according to the present invention preferably contains a cellulose derivative.
  • the cellulose derivative used in the present invention is a compound having a basic structure of cellulose, for example, a compound having a cellulose skeleton obtained by introducing a functional group biologically or chemically from cellulose as a raw material. To do.
  • cellulose derivative used in the present invention examples include cellulose ether (for example, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, cyanoethyl cellulose, etc.), cellulose ester (for example, triacetyl cellulose, diacetyl cellulose, cellulose acetate).
  • cellulose ether for example, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, cyanoethyl cellulose, etc.
  • cellulose ester for example, triacetyl cellulose, diacetyl cellulose, cellulose acetate
  • cellulose ether esters for example, acetyl methyl cellulose, acetyl ethyl cellulose, acetyl hydroxyethyl cellulose, benzoyl hydroxypropyl cellulose, etc.
  • Cellulose carbonate e.g. , And cellulose ethyl carbonate and the like
  • cellulose carbamates e.g., such as cellulose phenyl carbamate and the like
  • others as mentioned is preferably a cellulose ester.
  • two or more different types of cellulose derivatives may be mixed and used.
  • Cellulose ester The type of cellulose ester used in the present invention is not particularly limited, but is preferably a linear or branched carboxylic acid ester having 2 to 22 carbon atoms, and these carboxylic acids may form a ring. Further, it may be an ester of an aromatic carboxylic acid having 7 to 11 carbon atoms. In addition, these carboxylic acids may have a substituent.
  • the cellulose ester is particularly preferably a lower fatty acid ester having 6 or less carbon atoms.
  • More preferable cellulose ester types include, in addition to cellulose acetate, propionate groups or butyrate groups in addition to acetyl groups such as cellulose acetate propionate, cellulose acetate butyrate, and cellulose acetate propionate butyrate.
  • the total substitution degree of the acyl group of the cellulose ester used in the present invention is preferably 1.5 or more and 3.0 or less, and more preferably 1.5 or more and 2.6 or less.
  • the cellulose ester used in the present invention satisfies the following formulas (a) and (b) at the same time.
  • Formula (b) 0 ⁇ X ⁇ 2.6 (Wherein, X is the degree of substitution of the acetyl group, Y is the degree of substitution of the propionyl group or butyryl group, or a mixture thereof)
  • cellulose acetate it is preferable that 2.0 ⁇ X ⁇ 2.6, and as cellulose acetate propionate, 0 ⁇ X ⁇ 2.0, 0.5 ⁇ Y ⁇ 2.0, 1.5 ⁇ It is preferable that X + Y ⁇ 2.6.
  • the method for measuring the substitution degree of the acyl group can be measured according to ASTM-D817-96.
  • the portion not substituted with an acyl group usually exists as a hydroxyl group.
  • resins having different degrees of substitution may be mixed and used.
  • the mixing ratio is preferably 10:90 to 90:10 (mass ratio).
  • the number average molecular weight (Mn) of the cellulose derivative used in the present invention is preferably in the range of 30,000 to 200,000, and the resulting film has a high mechanical strength. Further, those having 40,000 to 100,000 are preferably used.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) of the cellulose derivative used in the present invention, preferably cellulose ester, can be measured using gel permeation chromatography (GPC).
  • the cellulose derivative used in the present invention preferably the cellulose ester, preferably has a weight average molecular weight (Mw) / number average molecular weight (Mn) value of 1.0 to 3.0.
  • the cellulose as a raw material for the cellulose derivative used in the present invention is not particularly limited, and examples thereof include cotton linter, wood pulp, and kenaf. Moreover, the cellulose derivative obtained from them can be mixed and used in arbitrary ratios, respectively.
  • cellulose derivatives used in the present invention preferably cellulose esters such as cellulose acetate and cellulose acetate propionate can be produced by known methods. Specifically, it can be synthesized with reference to the method described in JP-A-10-45804.
  • the resin that is the main component of the retardation film according to the present invention may further include other resins than the cellulose derivative.
  • Other resins include polycarbonate resins, polystyrene resins, polysulfone resins, polyester resins, polyarylate resins, acrylic resins (including copolymers), olefin resins (norbornene resins, cyclic olefin resins) And cyclic conjugated diene resins, vinyl alicyclic hydrocarbon resins, etc.), vinyl resins (including polyvinyl acetate resins, polyvinyl alcohol resins, etc.). Of these, acrylic resins are preferred as the resins that can be used in combination.
  • the content of the resin other than the cellulose derivative is preferably 5 to 70% by mass with respect to the entire resin.
  • the compound represented by the general formula (1) of the present invention can be contained by appropriately adjusting the amount for imparting a desired retardation to the film.
  • the addition amount of the compound represented by the general formula (1) is preferably 1 to 15% by mass, particularly preferably 2 to 10% by mass with respect to the cellulose derivative. If it exists in this range, sufficient retardation can be provided to the film containing a cellulose derivative.
  • the retardation film of the present invention is a plastic that imparts processability, flexibility, and moisture resistance to the film, which will be described below. It may further contain an agent, an ultraviolet absorber that imparts an ultraviolet absorbing function, an antioxidant that prevents deterioration of the film, and fine particles (matting agent) that impart slipperiness to the film.
  • Plasticizer The retardation film of the present invention can contain a plasticizer.
  • the plasticizer is not particularly limited, but is preferably a sugar ester plasticizer, a polyhydric alcohol ester plasticizer, a glycolate plasticizer, a phthalate ester plasticizer, a fatty acid ester plasticizer, or a phosphate ester plasticizer. Agent, polycarboxylic acid ester plasticizer, polyester plasticizer, vinyl polymer plasticizer, and the like. Two or more of these plasticizers can be used.
  • sugar ester compound examples include ester compounds in which at least one pyranose structure or furanose structure is 1 to 12 and all or part of the OH groups in the structure are esterified.
  • the proportion of esterification is preferably 50% or more of the OH groups present in the pyranose structure or furanose structure.
  • sugar ester compound used in the present invention examples include, but are not limited to, the following.
  • Glucose galactose, mannose, fructose, xylose or arabinose, lactose, sucrose, nystose, 1F-fructosyl nystose, stachyose, maltitol, lactitol, lactulose, cellobiose, maltose, cellotriose, maltotriose, raffinose or kestose .
  • gentiobiose gentiotriose
  • gentiotetraose gentiotetraose
  • xylotriose galactosyl sucrose
  • sucrose for example, sucrose, kestose, nystose, 1F-fructosyl nystose, stachyose and the like are preferable, and sucrose is more preferable.
  • the monocarboxylic acid used for esterifying all or part of the OH group in the pyranose structure or furanose structure is not particularly limited, and is a known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic A monocarboxylic acid or the like can be used.
  • the carboxylic acid used may be one type or a mixture of two or more types.
  • Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, lauric acid , Saturated fatty acids such as tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, and laccelic acid, Examples include unsaturated fatty acids such as undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid and oc
  • Examples of preferable alicyclic monocarboxylic acids include acetic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, and derivatives thereof.
  • aromatic monocarboxylic acids examples include aromatic monocarboxylic acids having an alkyl group or alkoxy group introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, cinnamic acid, benzylic acid, biphenylcarboxylic acid, and naphthalene.
  • aromatic monocarboxylic acids having two or more benzene rings such as carboxylic acid and tetralincarboxylic acid, or derivatives thereof.
  • Oligosaccharide ester compounds can be applied as compounds having 1 to 12 at least one pyranose structure or furanose structure.
  • Oligosaccharides are produced by allowing an enzyme such as amylase to act on starch, sucrose, etc.
  • examples of oligosaccharides that can be applied to the present invention include maltooligosaccharides, isomaltooligosaccharides, fructooligosaccharides, galactooligosaccharides, and xylooligos. Sugar.
  • sugar ester compounds examples are listed below, but the present invention is not limited thereto.
  • Monopet SB manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • Monopet SOA manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • the polyhydric alcohol ester plasticizer is a plasticizer composed of an ester of a divalent or higher aliphatic polyhydric alcohol and a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule.
  • a divalent to 20-valent aliphatic polyhydric alcohol ester is preferred.
  • the polyhydric alcohol preferably used in the present invention is represented by the following general formula (a).
  • Formula (a) Ra- (OH) r (where Ra is an r-valent organic group, r is a positive integer of 2 or more, and the OH group represents an alcoholic or phenolic hydroxyl group)
  • Examples of preferred polyhydric alcohols include the following, but the present invention is not limited to these.
  • Examples include 1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylolethane, pentaerythritol, dipentaerythritol, xylitol, inos
  • monocarboxylic acid used for polyhydric alcohol ester there is no restriction
  • Preferred examples of the monocarboxylic acid include the following, but the present invention is not limited to this.
  • aliphatic monocarboxylic acid a fatty acid having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used.
  • the number of carbon atoms is more preferably 1-20, and particularly preferably 1-10.
  • acetic acid is contained, compatibility with the cellulose derivative is increased, and it is also preferable to use a mixture of acetic acid and another monocarboxylic acid.
  • Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanoic acid, undecylic acid, lauric acid, tridecylic acid, Saturated fatty acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, laccelic acid, undecylenic acid, olein Examples thereof include unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid.
  • Examples of preferable alicyclic monocarboxylic acids include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, and derivatives thereof.
  • aromatic monocarboxylic acids examples include those in which 1 to 3 alkoxy groups such as alkyl group, methoxy group or ethoxy group are introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, biphenylcarboxylic acid, Examples thereof include aromatic monocarboxylic acids having two or more benzene rings such as naphthalenecarboxylic acid and tetralincarboxylic acid, or derivatives thereof. Benzoic acid is particularly preferable.
  • the molecular weight of the polyhydric alcohol ester is not particularly limited, but is preferably 300 to 1500, and more preferably 350 to 750. A higher molecular weight is preferable because it is less likely to volatilize, and a lower molecular weight is preferable in terms of moisture permeability and compatibility with cellulose derivatives.
  • the carboxylic acid used in the polyhydric alcohol ester may be one kind or a mixture of two or more kinds. Moreover, all the OH groups in the polyhydric alcohol may be esterified, or a part of the OH groups may be left as they are.
  • the glycolate plasticizer is not particularly limited, but alkylphthalylalkyl glycolates can be preferably used.
  • alkyl phthalyl alkyl glycolates include methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate, methyl phthalyl ethyl Glycolate, ethyl phthalyl methyl glycolate, ethyl phthalyl propyl glycolate, methyl phthalyl butyl glycolate, ethyl phthalyl butyl glycolate, butyl phthalyl methyl glycolate, butyl phthalyl ethyl glycolate, propyl phthalyl butyl glycol Butyl phthalyl propyl glycolate, methyl phthalyl octyl
  • phthalate ester plasticizer examples include diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, and dicyclohexyl terephthalate.
  • fatty acid ester plasticizers examples include butyl oleate, methylacetyl ricinoleate, and dibutyl sebacate.
  • phosphate ester plasticizer examples include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, and the like.
  • the polyvalent carboxylic acid ester compound is composed of an ester of a divalent or higher, preferably a divalent to 20valent polyvalent carboxylic acid and an alcohol.
  • the aliphatic polyvalent carboxylic acid is preferably divalent to 20-valent, and in the case of an aromatic polyvalent carboxylic acid or alicyclic polyvalent carboxylic acid, it is preferably trivalent to 20-valent.
  • the polyvalent carboxylic acid is represented by the following general formula (b).
  • General formula (b) Rb (COOH) m (OH) r (where Rb is a (m + r) -valent organic group, m is a positive integer of 2 or more, r is an integer of 0 or more, COOH group is a carboxyl group, OH The group represents an alcoholic or phenolic hydroxyl group.)
  • Preferred examples of the polyvalent carboxylic acid include the following, but the present invention is not limited to these.
  • Trivalent or higher aromatic polyvalent carboxylic acids such as trimellitic acid, trimesic acid, pyromellitic acid or derivatives thereof, succinic acid, adipic acid, azelaic acid, sebacic acid, oxalic acid, fumaric acid, maleic acid, tetrahydrophthal
  • An aliphatic polyvalent carboxylic acid such as an acid, an oxypolyvalent carboxylic acid such as tartaric acid, tartronic acid, malic acid and citric acid can be preferably used.
  • alcohol used for a polyhydric carboxylic acid ester compound there is no restriction
  • an aliphatic saturated alcohol or aliphatic unsaturated alcohol having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used. More preferably, it has 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms.
  • alicyclic alcohols such as cyclopentanol and cyclohexanol or derivatives thereof, aromatic alcohols such as benzyl alcohol and cinnamyl alcohol, or derivatives thereof can also be preferably used.
  • the alcoholic or phenolic hydroxyl group of the oxypolycarboxylic acid may be esterified with a monocarboxylic acid.
  • monocarboxylic acids include the following, but the present invention is not limited thereto.
  • aliphatic monocarboxylic acid a straight-chain or side-chain fatty acid having 1 to 32 carbon atoms can be preferably used. More preferably, it has 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms.
  • Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, lauric acid, tridecylic acid, Saturated fatty acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, and laccelic acid, undecylenic acid, olein Examples thereof include unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid.
  • Examples of preferable alicyclic monocarboxylic acids include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, and derivatives thereof.
  • aromatic monocarboxylic acids examples include those in which an alkyl group is introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, and two or more benzene rings such as biphenyl carboxylic acid, naphthalene carboxylic acid, and tetralin carboxylic acid. And aromatic monocarboxylic acids possessed by them, or derivatives thereof. Particularly preferred are acetic acid, propionic acid, and benzoic acid.
  • the molecular weight of the polyvalent carboxylic acid ester compound is not particularly limited, but is preferably in the range of 300 to 1000, and more preferably in the range of 350 to 750. The larger one is preferable in terms of improving the retention, and the smaller one is preferable in terms of moisture permeability and compatibility with the cellulose derivative.
  • the alcohol used for the polyvalent carboxylic acid ester may be one kind or a mixture of two or more kinds.
  • the acid value of the polyvalent carboxylic acid ester compound that can be used in the present invention is preferably 1 mgKOH / g or less, and more preferably 0.2 mgKOH / g or less. Setting the acid value in the above range is preferable because the environmental fluctuation of the retardation is also suppressed.
  • Acid value refers to the number of milligrams of potassium hydroxide necessary to neutralize the acid (carboxyl group present in the sample) contained in 1 g of the sample.
  • the acid value is measured according to JIS K0070.
  • Examples of particularly preferred polyvalent carboxylic acid ester compounds are shown below, but the present invention is not limited thereto.
  • the polyester plasticizer is not particularly limited, and a polyester plasticizer having an aromatic ring or a cycloalkyl ring in the molecule can be used. Although it does not specifically limit as a polyester plasticizer, for example, the compound represented with the following general formula (c) can be used.
  • the polyester plasticizer represented by the general formula (c) is an aliphatic monocarboxylic acid residue having 2 to 12 carbon atoms or an aromatic monocarboxylic acid residue having 7 to 15 carbon atoms represented by B and represented by G.
  • Examples of the aliphatic monocarboxylic acid residue having 2 to 12 carbon atoms or the aromatic monocarboxylic acid component having 7 to 15 carbon atoms of the polyester plasticizer used in the present invention include acetic acid, propionic acid, and cyclohexanecarboxylic acid.
  • alkylene glycol component having 2 to 12 carbon atoms of the polyester plasticizer examples include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,2-propanediol, 2-methyl 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (Neopentyl glycol), 2,2-diethyl-1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylol) Heptane), 3-methyl-1,5-pentanediol 1,6-hexanediol, 2,2,4-trimethyl 1, -Pentanedi
  • Examples of the cycloalkylene glycol component having 6 to 12 carbon atoms include 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, and the like. It is used as one kind or a mixture of two or more kinds.
  • Examples of the oxyalkylene glycol component having 4 to 12 carbon atoms include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol. These glycols are used as one kind or a mixture of two or more kinds. Can be used.
  • G is preferably an alkylene glycol having 2 to 12 carbon atoms because it has excellent compatibility with the cellulose derivative.
  • alkylene dicarboxylic acid component having 4 to 12 carbon atoms examples include succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and the like. These are used as one kind or a mixture of two or more kinds.
  • Examples of the cycloalkylene dicarboxylic acid component having 8 to 12 carbon atoms include 1,4-cyclohexanedicarboxylic acid, 2,6-decalin dicarboxylic acid, and the like. These dicarboxylic acids are used as one kind or a mixture of two or more kinds. used.
  • arylenedicarboxylic acid component having 8 to 12 carbon atoms examples include phthalic acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and 1,4-naphthalenedicarboxylic acid. These dicarboxylic acids are used as one kind or a mixture of two or more kinds.
  • the number average molecular weight of the polyester plasticizer used in the present invention is preferably 300 to 2000, more preferably 400 to 1500.
  • the acid value is 0.5 mgKOH / g or less
  • the hydroxyl value is 300 mgKOH / g or less, more preferably the acid value is 0.3 mgKOH / g or less, and the hydroxyl value is 250 mgKOH / g or less.
  • Example No. 1 In a nitrogen atmosphere, 410 parts of phthalic acid, 610 parts of benzoic acid, 737 parts of dipropylene glycol, and 0.40 part of tetraisopropyl titanate as a catalyst were charged all at once in a nitrogen atmosphere, and a reflux condenser was attached while stirring. Heating was continued at 130 to 250 ° C. until the acid value became 2 or less, and water produced was continuously removed. Next, the distillate is removed at 200-230 ° C. under reduced pressure of 1.33 ⁇ 10 4 Pa to finally 4 ⁇ 10 2 Pa or less, and then filtered to obtain a polyester plasticizer having the following properties. It was. Viscosity (25 ° C., mPa ⁇ s); 43400 Acid value: 0.2
  • Sample No. 4 was used except that 410 parts of phthalic acid, 610 parts of benzoic acid, 341 parts of ethylene glycol, and 0.35 part of tetraisopropyl titanate as a catalyst were used in a reaction vessel under a nitrogen atmosphere.
  • a polyester plasticizer having the following properties was obtained in exactly the same manner as in Example 1. Viscosity (25 ° C., mPa ⁇ s); 31000 Acid value: 0.1
  • Sample No. 4 was used except that 410 parts of phthalic acid, 610 parts of benzoic acid, 418 parts of 1,2-propanediol, and 0.35 part of tetraisopropyl titanate as a catalyst were used in a reaction vessel in a nitrogen atmosphere.
  • a polyester plasticizer having the following properties was obtained in exactly the same manner as in Example 1. Viscosity (25 ° C., mPa ⁇ s); 38000 Acid value: 0.05
  • Sample No. 4 was used except that 410 parts of phthalic acid, 610 parts of benzoic acid, 418 parts of 1,3-propanediol, and 0.35 part of tetraisopropyl titanate as a catalyst were used in a reaction vessel in a nitrogen atmosphere.
  • a polyester plasticizer having the following properties was obtained in exactly the same manner as in Example 1. Viscosity (25 ° C., mPa ⁇ s); 37000 Acid value: 0.05
  • Example No. 6 In a nitrogen atmosphere, 20.0 parts of dimethyl terephthalate, 18.8 parts of 1,2-propylene glycol, and 0.02 part of tetraisopropyl titanate were mixed in a reaction vessel, and the methanol produced was distilled off at 1 at 165 ° C. Stir for hours. The mixture was further stirred at 185 ° C. for 1 hour, then heated to 195 ° C. and stirred for 18 hours. Next, the temperature was lowered to 165 ° C., and unreacted 1,2-propylene glycol was distilled off under reduced pressure to obtain a polyester plasticizer having the following properties. Number average molecular weight: 1150 Acid value: 0.1 Hydroxyl value: 97
  • the vinyl polymer plasticizer is not particularly limited, and examples thereof include aliphatic hydrocarbon polymers, alicyclic hydrocarbon polymers, polyethyl acrylate, polymethyl methacrylate, methyl methacrylate and 2-hydroxyethyl methacrylate.
  • Acrylic polymers such as copolymers of methyl methacrylate and copolymers of N-acryloylmorpholine, vinyl ether polymers such as polyvinyl isobutyl ether, poly N-vinyl pyrrolidone, methyl methacrylate and N-vinyl pyrrolidone
  • Examples thereof include amide polymers such as copolymers, and styrene polymers such as polystyrene and poly-4-hydroxystyrene.
  • the number average molecular weight is preferably about 500 to 20,000, particularly preferably 1000 to 10,000. Two or more of the above polymers may be used in combination.
  • the amount of these plasticizers to be added is preferably 0.5 to 30% by mass, particularly 3 to 20% by mass, based on the cellulose derivative.
  • UV absorber is excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less from the viewpoint of preventing deterioration of the polarizer or the display device with respect to ultraviolet rays, and from the viewpoint of liquid crystal display properties, visible light having a wavelength of 400 nm or more. A thing with little absorption is preferable.
  • the ultraviolet absorber used in the present invention include benzotriazole compounds, triazine compounds, benzophenone compounds, cyanoacrylate compounds, salicylic acid ester compounds, nickel complex salts, and the like. Of these compounds, triazine-based compounds, benzophenone-based compounds are preferable. Further, ultraviolet absorbers described in JP-A Nos. 10-182621 and 8-337574, and polymer ultraviolet absorbers described in JP-A Nos. 6-148430 and 2003-113317 may be used.
  • benzotriazole ultraviolet absorbers include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzo Triazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5 Chlorobenzotriazole, 2- (2′-hydroxy-3 ′-(3 ′′, 4 ′′, 5 ′′, 6 ′′ -tetrahydrophthalimidomethyl) -5′-methylphenyl) benzotriazole, 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol), 2- (2'-hydroxy 3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-
  • TINUVIN 171, TINUVIN 900, TINUVIN 928, TINUVIN 360 (all manufactured by BASF Japan), LA31 (manufactured by ADEKA Corporation), RUVA-100 ( Otsuka Chemical).
  • triazine ultraviolet absorbers include 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hydroxyphenyl and oxirane [(C10- Reaction product with C16 mainly C12-C13 alkyloxy) methyl] oxirane, 2- (2,4-dihydroxyphenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine Reaction product of (2-ethylhexyl) -glycidic acid ester with 2,4-bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3,5-triazine
  • TINUVIN 400 TINUVIN 405, TINUVIN 460, TINUVIN 479 (all manufactured by BASF Japan) and the like can be mentioned.
  • benzophenone ultraviolet absorber examples include 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-) Hydroxy-5-benzoylphenylmethane) and the like, but is not limited thereto.
  • the ultraviolet absorber is preferably added in an amount of 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, and further 0.5 to 2% by mass based on the resin. It is preferable. Two or more of these may be used in combination.
  • the molecular structure of other additives such as plasticizers, antioxidants, acid scavengers, etc.
  • the benzotriazole structure, triazine structure or benzophenone structure may be part of the polymer or regularly pendant to the polymer. It may be introduced in a part of.
  • the conventionally known UV-absorbing polymer is not particularly limited, and examples thereof include a polymer obtained by homopolymerizing RUVA-93 (manufactured by Otsuka Chemical) and a polymer obtained by copolymerizing RUVA-93 with other monomers. . Specifically, PUVA-30M obtained by copolymerizing RUVA-93 and methyl methacrylate in a ratio (mass ratio) of 3: 7, and PUVA-50M copolymerized in a ratio of 5: 5 (mass ratio). It is done. Furthermore, the polymer etc. which are described in Unexamined-Japanese-Patent No. 2003-113317 are mentioned.
  • Antioxidants are also called deterioration inhibitors. When a liquid crystal image display device or the like is placed in a high humidity and high temperature state, the retardation film may be deteriorated.
  • the antioxidant has a role of delaying or preventing the retardation film from being decomposed by, for example, the residual solvent amount of halogen in the retardation film or phosphoric acid of the phosphoric acid plasticizer. It is preferable to make it contain in.
  • a hindered phenol compound is preferably used.
  • 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di- -T-butyl-4-hydroxyphenyl) propionate] triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3 -(3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino)- 1,3,5-triazine, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], oct Decyl-3- (3,5-di-t-butyl-4-hydroxyphenyl
  • 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3 -(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] is preferred.
  • hydrazine-based metal deactivators such as N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine and tris (2,4-di- A phosphorus processing stabilizer such as t-butylphenyl) phosphite may be used in combination.
  • the amount of these compounds added is preferably 0.01 to 1.0%, more preferably 0.05 to 0.5% in terms of mass ratio with respect to the cellulose derivative.
  • the retardation film according to the present invention preferably contains fine particles.
  • examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, and hydrated silicic acid. Mention may be made of calcium, aluminum silicate, magnesium silicate and calcium phosphate. Further, fine particles of an organic compound can also be preferably used.
  • organic compounds include polytetrafluoroethylene, cellulose acetate, polystyrene, polymethyl methacrylate, polypropyl methacrylate, polymethyl acrylate, polyethylene carbonate, acrylic styrene resin, silicone resin, polycarbonate resin, benzoguanamine resin, melamine resin
  • organic polymer compounds such as polyolefin-based powders, polyester-based resins, polyamide-based resins, polyimide-based resins, polyfluorinated ethylene-based resins, and starches.
  • a polymer compound synthesized by a suspension polymerization method, a polymer compound made spherical by a spray dry method or a dispersion method, or an inorganic compound can be used.
  • Fine particles containing silicon are preferable in terms of low turbidity, and silicon dioxide is particularly preferable.
  • Silicon dioxide fine particles are commercially available, for example, under the trade names Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.). it can.
  • Zirconium oxide fine particles are commercially available, for example, under the trade names Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.).
  • Examples of the polymer include silicone resin, fluororesin and acrylic resin. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, 105, 108, 120, 145, 3120 and 240 (manufactured by Toshiba Silicone Co., Ltd.) It is marketed by name and can be used.
  • Aerosil 200V and Aerosil R972V are particularly preferably used because they have a large effect of reducing the friction coefficient while keeping the turbidity of the retardation film low.
  • the dynamic friction coefficient of at least one surface is 0.2 to 1.0.
  • the average primary particle size of the fine particles is preferably 5 to 400 nm, and more preferably 10 to 300 nm. These may be mainly contained as secondary aggregates having a particle size of 0.05 to 0.3 ⁇ m, and may be contained as primary particles without being aggregated if the particles have an average particle size of 100 to 400 nm. preferable.
  • the content of these fine particles in the retardation film is preferably 0.01 to 1% by mass, particularly preferably 0.05 to 0.5% by mass.
  • additives may be batch-added to a dope that is a cellulose derivative-containing solution before film formation, or an additive solution may be separately prepared and added in-line.
  • an additive solution may be separately prepared and added in-line.
  • the additive solution When the additive solution is added in-line, it is preferable to dissolve a small amount of cellulose derivative in order to improve mixing with the dope.
  • the amount of the cellulose derivative is preferably 1 to 10 parts by mass, more preferably 3 to 5 parts by mass with respect to 100 parts by mass of the solvent.
  • an in-line mixer such as a static mixer (manufactured by Toray Engineering), SWJ (Toray static type in-tube mixer Hi-Mixer) or the like is preferably used.
  • the thickness of the retardation film according to the present invention is not particularly limited, but 10 to 80 ⁇ m is used. From the viewpoint of thinning, it is preferably 15 to 40 ⁇ m, and more preferably 20 to 35 ⁇ m. If the film thickness is within this range, it is preferable because both the expression of retardation by the compounds represented by the general formulas (1) to (4) according to the present invention, film mechanical strength, and durability can be achieved.
  • the retardation film means a film having a specific retardation in the in-plane direction and / or thickness direction of the film, preferably a film having a specific retardation (retardation) of 10 nm or more, more preferably 40 nm or more.
  • the retardation film according to the present invention can be used as an optical compensation film described below.
  • liquid crystal displays use anisotropic liquid crystal materials and polarizing plates, there is a viewing angle problem that even if a good display is obtained when viewed from the front, the display performance is degraded when viewed from an oblique direction.
  • a viewing angle compensator is necessary.
  • the average refractive index distribution is larger in the cell thickness direction and smaller in the in-plane direction. Therefore, a compensation plate that can cancel out this anisotropy and that has a so-called negative uniaxial structure in which the refractive index in the film thickness direction is smaller than that in the in-plane direction is effective.
  • the retardation film according to the present invention can also be used as an optical compensation film having such a function.
  • the retardation film according to the present invention When the retardation film according to the present invention is used for the VA mode, a mode in which a total of two sheets are used on each side of the cell (two-sheet type) and a mode in which only one of the upper and lower sides of the cell is used ( (Single sheet type) may be used.
  • the retardation film according to the present invention has an in-plane retardation Ro of 40 to 100 nm and a thickness direction retardation with respect to light having a wavelength of 590 nm in an environment of 23 ° C. and 55% RH. More preferably, Rth is 100 to 300 nm.
  • Formula (I) Ro (nx ⁇ ny) ⁇ d
  • Formula (II) Rth ⁇ (nx + ny) / 2 ⁇ nz ⁇ ⁇ d (where nx represents the refractive index in the direction x where the refractive index is maximum in the in-plane direction of the film, and ny is the in-plane direction of the film) )
  • nx represents the refractive index in the direction x where the refractive index is maximum in the in-plane direction of the film, and ny is the in-plane direction of the film
  • nz represents the refractive index in the thickness direction z of the film
  • d (nm) represents the thickness of the retardation film.
  • retardation values can be measured using an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments).
  • the slow axis or the fast axis exists in the film plane, and ⁇ 1 is preferably ⁇ 1 ° or more and + 1 ° or less when the angle formed with the film forming direction is ⁇ 1. More preferably, it is 0.5 ° or more and + 0.5 ° or less.
  • This ⁇ 1 can be defined as an orientation angle, and the measurement of ⁇ 1 can be performed using an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments).
  • Each of ⁇ 1 satisfying the above relationship can contribute to obtaining high luminance in a display image, suppressing or preventing light leakage, and contributing to obtaining faithful color reproduction in a color liquid crystal display device.
  • the water vapor permeability of the retardation film according to the present invention is preferably 10 to 1200 g / m 2 ⁇ 24 h at 40 ° C. and 90% RH.
  • the moisture permeability can be measured according to the method described in JIS Z 0208.
  • the retardation film according to the present invention preferably has a breaking elongation of 10 to 80%.
  • the visible light transmittance of the retardation film according to the present invention is preferably 90% or more, and more preferably 93% or more.
  • the haze of the retardation film according to the present invention is preferably less than 1%, particularly preferably 0 to 0.1%.
  • the retardation film according to the present invention can be preferably used regardless of whether it is a film produced by a solution casting method or a film produced by a melt casting method.
  • Production of the retardation film according to the present invention includes a step of dissolving a cellulose derivative and an additive in a solvent to prepare a dope, a step of casting a dope on an endless metal support, and a cast dope. Is performed by a step of drying as a web, a step of peeling from a metal support, a step of stretching or maintaining the width, a step of further drying, and a step of winding up the finished film.
  • the concentration of the cellulose derivative in the dope is preferably higher because the drying load after casting on the metal support can be reduced. However, if the concentration of the cellulose derivative is too high, the load during filtration increases and the filtration accuracy is poor. Become.
  • the concentration that achieves both of these is preferably 10 to 35% by mass, and more preferably 15 to 25% by mass.
  • Solvents used in the dope may be used alone or in combination of two or more. However, it is preferable to use a mixture of a good solvent and a poor solvent of a cellulose derivative in terms of production efficiency, and there are many good solvents. This is preferable from the viewpoint of the solubility of the cellulose derivative.
  • the preferable range of the mixing ratio of the good solvent and the poor solvent is 70 to 98% by mass for the good solvent and 2 to 30% by mass for the poor solvent.
  • dissolves the cellulose derivative to be used independently is defined as a good solvent, and what poorly swells or does not dissolve is defined as a poor solvent.
  • the good solvent and the poor solvent change depending on the average acetylation degree (acetyl group substitution degree) of the cellulose ester.
  • acetyl group substitution degree acetyl group substitution degree
  • cellulose diacetate acetyl group substitution degree 2.2 to 2.
  • Cellulose acetate propionate is a good solvent
  • cellulose triacetate acetyl group substitution degree: 2.7 to 2.9
  • the good solvent used in the present invention is not particularly limited, and examples thereof include organic halogen compounds such as methylene chloride, dioxolanes, acetone, methyl acetate, and methyl acetoacetate. Particularly preferred is methylene chloride or methyl acetate.
  • the poor solvent used in the present invention is not particularly limited, but for example, methanol, ethanol, n-butanol, cyclohexane, cyclohexanone and the like are preferably used.
  • the dope preferably contains 0.01 to 2% by mass of water.
  • the recovered solvent may contain trace amounts of additives added to the cellulose derivative, such as plasticizers, UV absorbers, polymers, monomer components, etc., but these are preferably reused even if they are included. Can be purified and reused if necessary.
  • a general method can be used. When heating and pressurization are combined, it is possible to heat above the boiling point at normal pressure. It is preferable to stir and dissolve while heating at a temperature that is equal to or higher than the boiling point of the solvent at normal pressure and that the solvent does not boil under pressure, in order to prevent the generation of massive undissolved materials called gels and macos.
  • a method in which a cellulose derivative is mixed with a poor solvent and wetted or swollen, and then a good solvent is added and dissolved is also preferably used.
  • Pressurization may be performed by a method of injecting an inert gas such as nitrogen gas or a method of developing the vapor pressure of the solvent by heating. Heating is preferably performed from the outside. For example, a jacket type is preferable because temperature control is easy.
  • the heating temperature with the addition of the solvent is preferably higher from the viewpoint of the solubility of the cellulose derivative, but if the heating temperature is too high, the required pressure increases and the productivity deteriorates.
  • a preferred heating temperature is 45 to 120 ° C, more preferably 60 to 110 ° C, and still more preferably 70 ° C to 105 ° C. The pressure is adjusted so that the solvent does not boil at the set temperature.
  • a cooling dissolution method is also preferably used, whereby the cellulose derivative can be dissolved in a solvent such as methyl acetate.
  • the cellulose derivative solution is filtered using an appropriate filter medium such as filter paper.
  • an appropriate filter medium such as filter paper.
  • the filter medium it is preferable that the absolute filtration accuracy is small in order to remove insoluble matters and the like, but there is a problem that the filter medium is likely to be clogged if the absolute filtration accuracy is too small. For this reason, a filter medium with an absolute filtration accuracy of 0.008 mm or less is preferable, a filter medium with 0.001 to 0.008 mm is more preferable, and a filter medium with 0.003 to 0.006 mm is more preferable.
  • the material of the filter medium there are no particular restrictions on the material of the filter medium, and ordinary filter media can be used.
  • plastic filter media such as polypropylene and Teflon (registered trademark), and metal filter media such as stainless steel do not drop off fibers. preferable. It is preferable to remove and reduce impurities, particularly bright spot foreign matter, contained in the raw cellulose derivative by filtration.
  • the bright spot foreign matter is arranged in a crossed Nicols state with two polarizing plates, a retardation film or the like is placed between them, light is applied from one polarizing plate side, and observation is performed from the other polarizing plate side. It is a point (foreign matter) where light from the opposite side sometimes leaks, and the number of bright spots having a diameter of 0.01 mm or more is preferably 200 / cm 2 or less. More preferably, it is 100 pieces / cm 2 or less, further preferably 50 pieces / cm 2 or less, and further preferably 0 to 10 pieces / cm 2 . Further, it is preferable that the number of bright spots of 0.01 mm or less is small.
  • the dope can be filtered by a normal method, but the method of filtering while heating at a temperature not lower than the boiling point of the solvent at normal pressure and in a range where the solvent does not boil under pressure is the filtration pressure before and after filtration.
  • the expression of the difference (referred to as differential pressure) is small and preferable.
  • a preferred temperature is 45 to 120 ° C., more preferably 45 to 70 ° C., and still more preferably 45 to 55 ° C.
  • the filtration pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, and further preferably 1.0 MPa or less.
  • the metal support in the casting process is preferably a mirror-finished surface, and a stainless steel belt or a drum whose surface is plated with a casting is preferably used as the metal support.
  • the cast width can be 1 to 4 m.
  • the surface temperature of the metal support in the casting step is ⁇ 50 ° C. to less than the boiling point of the solvent, and a higher temperature is preferable because the web drying speed can be increased. May deteriorate.
  • the support temperature is preferably 0 to 40 ° C, more preferably 5 to 30 ° C.
  • it is also a preferable method that the web is gelled by cooling and peeled from the drum in a state containing a large amount of residual solvent.
  • the method for controlling the temperature of the metal support is not particularly limited, and there are a method of blowing hot air or cold air, and a method of contacting hot water with the back side of the metal support. It is preferable to use warm water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short. When warm air is used, wind at a temperature higher than the target temperature may be used.
  • the amount of residual solvent when peeling the web from the metal support is preferably 10 to 150% by mass, more preferably 20 to 40% by mass or 60 to 130% by mass. Particularly preferred is 20 to 30% by mass or 70 to 120% by mass.
  • the web is peeled off from the metal support and further dried, and the residual solvent amount is preferably 1% by mass or less, more preferably 0.1% by mass or less, Particularly preferred is 0 to 0.01% by mass or less.
  • a roll drying method (a method in which webs are alternately passed through a plurality of rolls arranged above and below) and a method in which the web is dried while being conveyed by a tenter method are employed.
  • the retardation film according to the present invention it is particularly preferable to stretch in the width direction (lateral direction) by a tenter method in which both ends of the web are gripped by clips or the like. Peeling is preferably performed at a peeling tension of 300 N / m or less.
  • the means for drying the web is not particularly limited, and can be generally performed with hot air, infrared rays, a heating roll, microwave, or the like, but is preferably performed with hot air from the viewpoint of simplicity.
  • drying temperature in the web drying process is increased stepwise from 40 to 200 ° C.
  • the retardation film according to the present invention has a width of 1 to 4 m. Particularly, those having a width of 1.4 to 4 m are preferably used, and particularly preferably 1.6 to 3 m. If it exceeds 4 m, conveyance becomes difficult.
  • biaxial stretching or uniaxial stretching can be performed sequentially or simultaneously with respect to the longitudinal direction (film forming direction) of the film and the direction orthogonal to the longitudinal direction of the film, that is, the width direction.
  • Simultaneous biaxial stretching includes stretching in one direction and contracting the other while relaxing the tension.
  • the draw ratios in the biaxial directions perpendicular to each other are preferably in the range of 0.8 to 1.5 times in the casting direction and 1.1 to 2.5 times in the width direction, respectively. It is preferable to carry out in the range of 0.9 to 1.0 times in the direction and 1.2 to 2.0 times in the width direction.
  • the stretching temperature is preferably 120 ° C. to 200 ° C., more preferably 140 ° C. to 180 ° C.
  • the residual solvent in the film during stretching is preferably 20 to 0%, more preferably 15 to 0%.
  • the method of stretching the web For example, a method in which a difference in peripheral speed is applied to a plurality of rolls, and the roll peripheral speed difference is used to stretch in the longitudinal direction, the both ends of the web are fixed with clips and pins, and the interval between the clips and pins is increased in the traveling direction. And a method of stretching in the vertical direction, a method of stretching in the horizontal direction and stretching in the horizontal direction, a method of stretching in the vertical and horizontal directions and stretching in both the vertical and horizontal directions. Of course, these methods may be used in combination. In the case of the so-called tenter method, driving the clip portion by the linear drive method is preferable because smooth stretching can be performed and the risk of breakage and the like can be reduced.
  • a tenter it may be a pin tenter or a clip tenter.
  • a retardation value over a wider range can be obtained by further applying a liquid crystal layer or a resin layer to the retardation film according to the present invention, or by further stretching it.
  • the retardation film according to the present invention can be used for the polarizing plate of the present invention and the liquid crystal display device of the present invention using the polarizing plate.
  • the retardation film according to the present invention is preferably a film that also functions as a polarizing plate protective film. In that case, it is not necessary to separately prepare an optical film having a phase difference separately from the polarizing plate protective film.
  • the manufacturing process can be simplified by reducing the thickness of the display device.
  • the polarizing plate of the present invention has a polarizer and the retardation film of the present invention disposed on at least one surface thereof.
  • the retardation film of the present invention may be disposed directly on the surface of the polarizer, or may be disposed via another layer or film.
  • a polarizer which is a main component of a polarizing plate, is an element that allows only light of a plane of polarization in a certain direction to pass.
  • a typical polarizer currently known is a polyvinyl alcohol-based polarizing film, which is polyvinyl alcohol.
  • iodine is dyed on a system film and one in which dichroic dye is dyed.
  • the polarizer is formed by forming a polyvinyl alcohol aqueous solution into a film and dyeing the film by uniaxial stretching or dyeing or uniaxially stretching, and then performing a durability treatment with a boron compound.
  • the film thickness of the polarizer is preferably 5 to 30 ⁇ m, particularly preferably 10 to 20 ⁇ m.
  • the polarizing plate according to the present invention can be produced by a general method.
  • the polarizer side of the retardation film according to the present invention is preferably bonded to at least one surface of a polarizer prepared by alkali saponification treatment and immersion-drawn in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution. .
  • Another polarizing plate protective film can be bonded to the other surface.
  • the retardation film according to the present invention is a liquid crystal display device, it is preferably provided on the liquid crystal cell side of the polarizer, and a conventional polarizing plate protective film can be used as the film outside the polarizer.
  • a commercially available cellulose ester film for example, Konica Minoltak KC8UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC6UY, KC4UY, KC4UA, KC4UE, KC4CZ, C8- KC8UX-RHA, KC8UXW-RHA-C, KC8UXW-RHA-NC, KC4UXW-RHA-NC, manufactured by Konica Minolta Opto Co., Ltd.
  • a commercially available cellulose ester film for example, Konica Minoltak KC8UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC6UY, KC4UY, KC4UA, KC4UE, KC4CZ, C8- KC8UX-RHA, KC8UXW-R
  • the polarizing plate protective film used on the surface side of the display device preferably has an antireflection layer, an antistatic layer, an antifouling layer, and a backcoat layer in addition to the antiglare layer or the clear hard coat layer.
  • the liquid crystal display device of the present invention includes the retardation film of the present invention.
  • the liquid crystal display device of the present invention has a liquid crystal cell and a pair of polarizing plates sandwiching the liquid crystal cell; at least one of the pair of polarizing plates is the polarizing plate of the present invention; preferably both Is the polarizing plate of the present invention. It is preferable that the polarizing plate and the liquid crystal cell of the present invention are bonded together via an adhesive layer.
  • the retardation film according to the present invention is preferably disposed on the surface of the polarizer on the liquid crystal cell side.
  • the liquid crystal cell may be a liquid crystal cell of various drive systems such as STN, TN, OCB, HAN, VA (MVA, PVA), IPS, OCB, and particularly a VA (MVA, PVA) type liquid crystal cell. preferable.
  • the liquid crystal display device including the retardation film of the present invention is excellent in visibility such as front contrast because coloring at the time of black display due to light leakage is reduced even if the screen is a large screen of 30 type or more.
  • Cellulose derivative A Cellulose diacetate having an acetyl substitution degree of 2.42 (acyl group total substitution degree 2.42; described as DAC in the table)
  • Cellulose derivative B cellulose triacetate having an acetyl substitution degree of 2.88 (acyl group total substitution degree 2.88, described as TAC in the table)
  • Cellulose derivative C cellulose acetate propionate having an acetyl substitution degree of 1.56 and a propionyl substitution degree of 0.90 (acyl group total substitution degree 2.46, described as CAP1 in the table)
  • Cellulose derivative D cellulose acetate propionate having an acetyl substitution degree of 0.21 and a propionyl substitution degree of 1.62 (acyl group total substitution degree of 1.83, described as CAP2 in the table)
  • Cellulose derivative E cellulose acetate propionate having an acetyl substitution degree of 1.50 and a propionyl substitution degree of 0.70 (acyl group total substitution degree 2.20, described as
  • Fine particle dispersion 1 was slowly added to the dissolution tank containing methylene chloride with sufficient stirring. Further, the particles were dispersed by an attritor so that the secondary particles had a predetermined particle size. This was filtered with Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution 1.
  • Composition of fine particle additive liquid 1 Methylene chloride: 99 parts by mass Fine particle dispersion 1: 5 parts by mass
  • a dope solution having the following composition was prepared. First, methylene chloride and ethanol were added to the pressure dissolution tank. Cellulose derivative A, exemplary compound 1, monopet SB, and fine particle additive solution 1 were added to a pressure dissolution tank containing a solvent while stirring. This was heated and dissolved completely with stirring. The obtained solution was used as Azumi filter paper No. manufactured by Azumi Filter Paper Co., Ltd. A dope solution was prepared by filtration using 244.
  • the obtained dope solution was uniformly cast on a stainless steel belt support at a temperature of 33 ° C. and a width of 1500 mm.
  • the temperature of the stainless steel belt was controlled at 30 ° C.
  • the solvent was evaporated until the residual solvent amount in the cast (cast) dope film became 75% to obtain a web.
  • the obtained web was peeled from the stainless steel belt support with a peeling tension of 130 N / m.
  • the web obtained by peeling was stretched 35% (1.35 times) in the width direction using a tenter while applying heat at 145 ° C.
  • the residual solvent at the start of stretching was 15%.
  • drying of the obtained film was terminated while being transported by a number of rolls in the drying zone.
  • the drying temperature was 130 ° C. and the transport tension was 100 N / m.
  • a retardation film 101 having a dry film thickness of 20 ⁇ m was obtained.
  • Example 2 to 27 and Comparative Examples 1 to 7 In the production of the phase difference film 101, Example 1 except that the kind of cellulose derivative, the compound represented by the general formula (1) according to the present invention, and other additives were used as shown in Table 1. In the same manner, retardation films 102 to 134 were produced.
  • the retardation Ro in the in-plane direction and the retardation Rth in the thickness direction at the center in the width direction of the obtained retardation film were measured by the following methods. 1) The obtained retardation film was conditioned for 2 hours in an environment of 23 ° C. and 55% RH. 2) Ro when light having a wavelength of 590 nm was incident on the retardation film after humidity control in parallel to the normal of the film surface was measured with KOBRA21ADH manufactured by Oji Scientific Instruments.
  • the slow axis in the plane of the retardation film is the tilt axis (rotation axis), and the measurement wavelength is 590 nm from the angle of ⁇ (incident angle ( ⁇ )) with respect to the normal of the surface of the retardation film.
  • the retardation value R ( ⁇ ) when light was incident was measured.
  • the retardation value R ( ⁇ ) was measured at 6 points every 10 °, with ⁇ ranging from 0 ° to 50 °.
  • the in-plane slow axis of the retardation film was confirmed by KOBRA21ADH.
  • nx, ny, and nz were calculated by KOBRA21ADH from the measured Ro and R ( ⁇ ) and the above-described average refractive index and film thickness, and Rth at a wavelength of 590 nm was calculated based on the following formula. .
  • the retardation was measured under the conditions of 23 ° C. and 55% RH.
  • Formula (I): Ro (nx ⁇ ny) ⁇ d
  • Rth ((nx + ny) / 2 ⁇ nz) ⁇ d (Where d represents the thickness of the film (nm); nx represents the maximum refractive index in the plane of the film (also referred to as the refractive index in the slow axis direction); ny represents the slow axis in the film plane) (Refer to the refractive index in the direction perpendicular to nz; nz indicates the refractive index in the thickness direction of the film)
  • the fluctuation range ⁇ Ro with respect to the humidity change of the retardation was ranked into the following levels.
  • B level or more there is no practical problem, but it may be A level. Particularly preferred.
  • Failure rate (%) (number of samples in which defects occurred / number of all cut out samples (100)) ⁇ 100
  • the slitting aptitude was evaluated according to the following criteria.
  • the durability of the retardation film was evaluated by the bleed-out resistance described below. That is, the retardation film was allowed to stand for 1000 hours in a high-temperature and high-humidity atmosphere at 80 ° C. and 90% RH, and then the presence or absence of bleed-out (crystal precipitation) on the surface of the retardation film was visually observed.
  • the bleed-out resistance was evaluated according to the following criteria. A: No bleed-out is observed on the surface B: Partial bleed-out is slightly observed on the surface C: Slight bleed-out is observed on the entire surface D: On the entire surface
  • a clear bleed out is recognized.
  • the level is B level or higher, there is no practical problem, but the level A is particularly preferable.
  • the retardation film was cut into 5 cm ⁇ 24 cm to obtain a sample film.
  • the obtained sample film was immersed in 40 g of a 1.5 mol / L potassium hydroxide aqueous solution at 70 ° C. for 30 hours.
  • an absorption spectrum of a potassium hydroxide aqueous solution in which the sample film was immersed for 30 hours was measured using a Hitachi Technologies spectrophotometer U-3310, and tristimulus values X, Y, and Z were calculated. From these tristimulus values X, Y and Z, the yellowness YI was calculated based on JIS-K7103, and the saponification liquid coloring was ranked according to the following criteria.
  • the retardation films 101 to 127 of Examples 1 to 27 are excellent in retardation development and mechanical strength (compared to the retardation films 128 to 134 of Comparative Examples 1 to 7). It can be seen that the film is a practically excellent retardation film having excellent brittleness) and durability (resistance to changes in humidity of retardation, bleed-out resistance, and alkali solution resistance).
  • Example 28 to 31 In the production of the retardation film 121 of Example 21, the addition amount of the exemplary compound 201 was changed as shown in Table 3, and the flow rate of the dope solution at the time of casting so as to have a film thickness as shown in Table 3 Retardation films 201 to 204 were produced in the same manner as in the production of the retardation film 121 of Example 21, except that the above was changed, and the same evaluation as in Example 21 was performed.
  • the retardation films 201 to 204 of Examples 28 to 31 are excellent in retardation development, mechanical strength (brittleness), and durability (resistance to changes in humidity of the retardation, bleeding) It can be seen that it is excellent in out resistance and alkali solution resistance).
  • the retardation films 121, 202, and 203 having a film thickness in the range of 20 to 35 ⁇ m have excellent effects.
  • a polarizer, the retardation film 101, and Konica Minolta Tack KC4UY were bonded to the back side to prepare a polarizing plate.
  • Step 1 The retardation film 101 was immersed in a 2 mol / L sodium hydroxide solution at 60 ° C. for 90 seconds, then washed with water and dried to saponify the side to be bonded to the polarizer.
  • Step 2 The polarizer was immersed in a polyvinyl alcohol adhesive tank having a solid content of 2% by mass for 1 to 2 seconds.
  • Step 3 Excess adhesive adhered to the polarizer in Step 2 was lightly wiped off and placed on the retardation film treated in Step 1.
  • Step 4 The Konica Minol Tack KC4UY was overlaid on the surface of the polarizer obtained in Step 3 opposite to the phase difference film to obtain a laminate. This laminate was bonded at a pressure of 20 to 30 N / cm 2 and a conveying speed of about 2 m / min.
  • Step 5 A sample obtained by bonding the polarizer, the retardation film, and the Konica Minoltack KC4UY prepared in Step 4 in a dryer at 80 ° C. was dried for 2 minutes to prepare the corresponding polarizing plate 101.
  • Polarizing plates 102 to 134 and 202 to 204 were produced in the same manner as in Example 32 except that the retardation film 101 was changed as shown in Table 4.
  • Reworkability (polarizing plate yield)
  • the produced polarizing plate was cut into a square having a size of 20 cm ⁇ 20 cm, and bonded to a glass substrate using an acrylic adhesive.
  • the bonded polarizing plate was peeled off from the glass with a strength of 5N from the corner. This operation was performed on 100 samples for each type of polarizing plate.
  • the number of polarizing plates that had cracks in the polarizing plate and was not completely peeled off was counted.
  • Reworkability was ranked according to the following criteria.
  • D 16 sheets or more
  • the parallel transmittance (H0) and the direct transmittance (H90) of the polarizing plate sample before the forced deterioration treatment were measured, and the degree of polarization P0 was calculated according to the following equation. Thereafter, the polarizing plate sample was subjected to forced deterioration treatment with a sunshine weather meter for 500 hours under the condition without a UV cut filter. Thereafter, the parallel transmittance (H0 ′) and the direct transmittance (H90 ′) of the polarizing plate sample after the forced deterioration treatment were measured again, and the degree of polarization P500 was calculated according to the following equation. And the variation
  • the amount of change in polarization degree obtained as described above was determined according to the following criteria, and light resistance was evaluated.
  • B level or more there is no practical problem, but it is particularly preferable that it is A level.
  • the “white-out portion” to be evaluated was the longest among a plurality of white-out portions generated near the center of each of the four edge portions of the polarizing plate sample.
  • the white edge of the edge is caused by the state where the edge of the polarizing plate that does not transmit light in the orthogonal state is in a state of transmitting light, causing a failure in which no image is displayed at the edge of the polarizing plate.
  • the wet heat resistance of the polarizing plate was evaluated based on the following criteria.
  • B level or more there is no practical problem, but it is particularly preferable that it is A level.
  • the polarizing plates 101 to 127 and 201 to 204 of Examples 32 to 62 have mechanical strength (reworkability) and durability compared to the polarizing plates 128 to 134 of Comparative Examples 8 to 14. It can be seen that (light resistance, heat and humidity resistance) is excellent.
  • liquid crystal display device Example 63
  • a liquid crystal panel for viewing angle measurement was produced as follows, and the characteristics as a liquid crystal display device were evaluated.
  • the polarizing plates on both sides of the 40-inch display KLV-40J3000 made by SONY were peeled off in advance, and the polarizing plates 101 produced in Example 32 were bonded to both surfaces of the glass surface of the liquid crystal cell, respectively.
  • the polarizing plates were bonded so that the surface of the retardation film of the present invention was on the liquid crystal cell side.
  • the polarizing plates were bonded so that the absorption axis of the produced polarizing plate and the absorption axis of the polarizing plate bonded in advance were in the same direction. Thereby, the liquid crystal display device 101 was produced.
  • Liquid crystal display devices 102 to 134 and 202 to 204 were produced in the same manner as in Example 63 except that the retardation film 101 was changed as shown in Table 5.
  • the liquid crystal display device produced as described above was evaluated as described below. The results are shown in Table 5.
  • Front contrast unevenness The backlight of the liquid crystal display device was lit continuously for one week in an environment of 23 ° C. and 55% RH. Then, the luminance in the direction parallel to the normal line of the display screen when the liquid crystal display device is displayed in black and the luminance in the direction parallel to the normal line of the display screen when white display is made by ELDIM Measurement was performed using EZ-Contrast 160D. The obtained brightness was applied to the following formula to calculate the front contrast.
  • Front contrast brightness of white display measured from the normal direction of the display screen / brightness of black display measured from the normal direction of the display screen
  • the front contrast at any five points on the display screen was measured. Then, the average value of the five front contrasts obtained was obtained. Further, among the five front contrasts obtained, the maximum value or the minimum value of the front contrast that maximizes the difference (absolute value) from the average value was obtained. These values were applied to the following formula to determine the front contrast variation (%).
  • Variation in front contrast (%)
  • the front contrast unevenness was evaluated according to the following criteria.
  • C Front contrast variation is 10% or more and unevenness
  • a level is particularly preferable.
  • the viewing angle of the liquid crystal display device after standing for 5 hours in an environment of 23 ° C. and 55% RH was measured using EZ-Contrast 160D manufactured by ELDIM. Next, the liquid crystal display device was left in an environment of 23 ° C. and 20% RH for 5 hours, and then the viewing angle was measured. Further, this liquid crystal display device was left in an environment of 23 ° C. and 80% RH for 5 hours, and then the viewing angle was measured. Finally, the liquid crystal display device was left in an environment of 23 ° C. and 55% RH for 5 hours, and then the viewing angle was measured. Then, the viewing angle measured in the first environment at 23 ° C.
  • the evaluation of the viewing angle variation was performed based on the following criteria. A: No viewing angle variation is observed B: Viewing angle variation is slightly recognized C: Viewing angle variation is recognized Here, if it is B level or more, there is no practical problem, but the A level is particularly preferable.
  • the liquid crystal display devices 101 to 127 and 201 to 204 of Examples 63 to 93 using the polarizing plates 101 to 127 and 201 to 204 of the present invention were compared using the polarizing plates 128 to 134.
  • the viewing angle is wide, there is no front contrast unevenness, and there is no viewing angle variation even under conditions where the humidity varies. It turns out that it is.

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Abstract

L'objet de la présente invention est de proposer un film de retard qui présente une capacité élevée de développement d'un retard, une bonne résistance mécanique et une bonne durabilité. Ce film de retard contient un dérivé de cellulose et au moins un composé représenté par la formule générale (1). (Dans la formule générale (1), chacun de R1 et R2 représente indépendamment un groupe alkyle, un groupe cycloalkyle, un groupe aryle ou un groupe hétérocyclique; X1 représente une liaison simple, -NR4-, -O- ou -S-; X2 représente une liaison simple, -NR5-, -NR5-(C=O)-, -O- ou -S-; chacun de R4 et R5 représente indépendamment un atome d'hydrogène, un groupe alkyle, un groupe cycloalkyle, un groupe aryle ou un groupe hétérocyclique; R3 représente un substituant; n représente un entier de 0 à 4; et lorsque n vaut 2 ou plus, plusieurs fractions de R3 peuvent être identiques ou différentes entre elles et des fractions adjacentes de R3 peuvent se combiner pour former un cycle.)
PCT/JP2012/001641 2011-03-10 2012-03-09 Film de retard, plaque polarisante, dispositif d'affichage à cristaux liquides et composé WO2012120897A1 (fr)

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CN201280022415.8A CN103518151B (zh) 2011-03-10 2012-03-09 相位差膜、偏振片、液晶显示装置及化合物
KR1020137023539A KR101558722B1 (ko) 2011-03-10 2012-03-09 위상차 필름, 편광판, 액정 표시 장치 및 화합물
US14/003,565 US8936840B2 (en) 2011-03-10 2012-03-09 Retardation film, polarizing plate, liquid crystal display device, and compound
JP2013503402A JP5920336B2 (ja) 2011-03-10 2012-03-09 位相差フィルム、偏光板、液晶表示装置及び化合物

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013125419A1 (fr) * 2012-02-22 2013-08-29 コニカミノルタ株式会社 Film optique, polariseur et dispositif d'affichage à cristaux liquides
WO2013125420A1 (fr) * 2012-02-22 2013-08-29 コニカミノルタ株式会社 Film optique, plaque polarisante et dispositif d'affichage à cristaux liquides
JP2013185100A (ja) * 2012-03-08 2013-09-19 Adeka Corp セルロース系樹脂組成物及びフィルム
JP2014240906A (ja) * 2013-06-12 2014-12-25 コニカミノルタ株式会社 偏光板とその製造方法、及びそれを具備した有機エレクトロルミネッセンス表示装置
JP2014240905A (ja) * 2013-06-12 2014-12-25 コニカミノルタ株式会社 偏光板とその製造方法、及びそれを具備した有機エレクトロルミネッセンス表示装置
WO2015060167A1 (fr) * 2013-10-24 2015-04-30 コニカミノルタ株式会社 Film à différence de phase, plaque de polarisation et dispositif d'affichage à cristaux liquides

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7956344B2 (en) 2007-02-27 2011-06-07 Macronix International Co., Ltd. Memory cell with memory element contacting ring-shaped upper end of bottom electrode
JP6277066B2 (ja) * 2014-05-30 2018-02-07 富士フイルム株式会社 光学フィルム、偏光板および液晶表示装置
US10759872B2 (en) 2016-04-22 2020-09-01 Eastman Chemical Company Regioselectively substituted cellulose esters and films made therefrom
CN115785002B (zh) * 2022-12-07 2024-10-11 枣庄学院 一种喹唑啉杂环衍生物的合成方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000111914A (ja) * 1998-09-30 2000-04-21 Fuji Photo Film Co Ltd セルロースの低級脂肪酸エステルフイルム用レターデーション上昇剤、光学補償シートおよび液晶表示装置
JP2002187958A (ja) * 2000-12-19 2002-07-05 Konica Corp セルロースエステルフィルムの製造方法、セルロースエステルフィルム及び偏光板
JP2008274246A (ja) * 2007-03-30 2008-11-13 Fujifilm Corp 紫外線吸収剤
JP2009523256A (ja) * 2006-01-13 2009-06-18 クリスオプティクス株式会社 有機化合物、異方性光学膜及びその製造方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3772274A (en) 1970-12-23 1973-11-13 Du Pont Process for preparing 2-(o-hydroxyphenyl)quinazolines
US5874438A (en) * 1996-10-11 1999-02-23 Bayer Aktiengesellschaft 2,2'-bridged bis-2,4-diaminoquinazolines
JP2002187358A (ja) * 2000-12-21 2002-07-02 Toppan Forms Co Ltd 情報担持用シート
JP5135657B2 (ja) * 2001-08-01 2013-02-06 コニカミノルタホールディングス株式会社 有機エレクトロルミネッセンス素子及び表示装置
JP2006096875A (ja) 2004-09-29 2006-04-13 Fuji Photo Film Co Ltd セルロース誘導体組成物、セルロース誘導体フイルム、およびビス型１，３，５−トリアジン誘導体化合物
WO2006104118A1 (fr) * 2005-03-29 2006-10-05 Konica Minolta Holdings, Inc. Dispositif electroluminescent organique, dispositif d’affichage et dispositif d’eclairage
EP1898238A4 (fr) * 2005-05-25 2017-04-05 Toray Industries, Inc. Film de retard et résine de polyester à usage optique
MX2008000745A (es) * 2005-07-15 2008-03-14 Schering Corp Derivados de quinazolina utiles en el tratamiento del cancer.
JP5208794B2 (ja) 2008-08-27 2013-06-12 富士フイルム株式会社 セルロースアシレートフィルム、光学補償フィルム、偏光板、及び液晶表示装置
JP2010170128A (ja) 2008-12-26 2010-08-05 Fujifilm Corp セルロースアシレートフィルム、偏光板及び液晶表示装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000111914A (ja) * 1998-09-30 2000-04-21 Fuji Photo Film Co Ltd セルロースの低級脂肪酸エステルフイルム用レターデーション上昇剤、光学補償シートおよび液晶表示装置
JP2002187958A (ja) * 2000-12-19 2002-07-05 Konica Corp セルロースエステルフィルムの製造方法、セルロースエステルフィルム及び偏光板
JP2009523256A (ja) * 2006-01-13 2009-06-18 クリスオプティクス株式会社 有機化合物、異方性光学膜及びその製造方法
JP2008274246A (ja) * 2007-03-30 2008-11-13 Fujifilm Corp 紫外線吸収剤

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013125419A1 (fr) * 2012-02-22 2013-08-29 コニカミノルタ株式会社 Film optique, polariseur et dispositif d'affichage à cristaux liquides
WO2013125420A1 (fr) * 2012-02-22 2013-08-29 コニカミノルタ株式会社 Film optique, plaque polarisante et dispositif d'affichage à cristaux liquides
JP2013185100A (ja) * 2012-03-08 2013-09-19 Adeka Corp セルロース系樹脂組成物及びフィルム
JP2014240906A (ja) * 2013-06-12 2014-12-25 コニカミノルタ株式会社 偏光板とその製造方法、及びそれを具備した有機エレクトロルミネッセンス表示装置
JP2014240905A (ja) * 2013-06-12 2014-12-25 コニカミノルタ株式会社 偏光板とその製造方法、及びそれを具備した有機エレクトロルミネッセンス表示装置
WO2015060167A1 (fr) * 2013-10-24 2015-04-30 コニカミノルタ株式会社 Film à différence de phase, plaque de polarisation et dispositif d'affichage à cristaux liquides
TWI570167B (zh) * 2013-10-24 2017-02-11 Konica Minolta Inc Phase difference film, polarizing plate and liquid crystal display device
JPWO2015060167A1 (ja) * 2013-10-24 2017-03-09 コニカミノルタ株式会社 位相差フィルム、偏光板及び液晶表示装置

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JPWO2012120897A1 (ja) 2014-07-17
CN103518151A (zh) 2014-01-15
US20130335685A1 (en) 2013-12-19
KR20130130041A (ko) 2013-11-29
US8936840B2 (en) 2015-01-20
KR101558722B1 (ko) 2015-10-07
CN103518151B (zh) 2016-09-28

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